Ink composition and recording method

ABSTRACT

An ink composition has a viscosity of 25 mPa·s to 35 mPa·s at 20° C., wherein a, b, and c are 800 or more, 7.4 to 14, and 0.16 to 0.22, respectively, when a cylindrical portion is formed by expanding the ink composition so as to have a free surface parallel to the expanding direction of the ink composition, the rate of change in width of the cylindrical portion with time is measured in the expanding direction thereof, and the rate of change in width of the cylindrical portion with time is fit to a quadratic function given by the following equation:
 
 S=−at   2   −bt+c   (1)
 
where S is the rate of change in width of the cylindrical portion and t is the time in seconds.

This application is a continuation of and claims priority to U.S. patentapplication Ser. No. 14/336,018 filed Jul. 21, 2014, which is acontinuation of and claims priority to U.S. patent application Ser. No.13/049,415, filed Mar. 16, 2011, U.S. Pat. No. 8,820,906, which claimspriority under 35 U.S.C. §119 to Japanese Patent Application No.2010-058885 filed Mar. 16, 2010, each of which is hereby incorporated byreference in its entirety.

BACKGROUND

1. Technical Field

The present invention relates to an ink composition and a recordingmethod.

2. Related Art

In recent years, techniques for forming images using photocurable inkcompositions curable with light such as ultraviolet light have beenwidely used for printing by ink jet recording. The use of suchphotocurable ink compositions allows images having high colordevelopability and weather resistance to be formed on, for example,recording media having low ink absorbency.

A photocurable ink composition usually contains a colorant, apolyfunctional monomer, and an ultraviolet polymerization initiator atleast and is designed to exhibit desired performance by controlling thetype, content, and/or combination of these compounds.

Methods for ejecting ink compositions from ink jet recording heads toapply the ink compositions to recording media need to be capable offorming fine images. Therefore, for example, attempts have been made toincrease the density of nozzles for ejecting ink and to reduce thevolume of droplets of ejected ink compositions as disclosed inJP-A-2008-179076.

Photocurable ink compositions contain high-viscosity compounds orhigh-molecular weight compounds, such as polymers or oligomers, forincreasing the performance of the photocurable ink compositions in somecases. When the photocurable ink compositions contain such compounds,heads for ejecting the photocurable ink compositions need to haveincreased discharge capacity.

In the development of such ink compositions, the type and/or amount ofcomponents contained in the ink compositions is limited depending on,for example, head capacity. Even if heads have a discharge capacitysufficiently large with respect to the type and amount of desiredcomponents, the heads fail to form ink droplets in some cases. Forexample, when an ink composition is ejected from nozzles, droplets ofthe ink composition are unlikely to fly separately or fine droplets(satellites) other than desired droplets are formed in some cases. Thisleads to a reduction in quality of an image to be recorded.

The inventors have made investigations on the basis of the idea that acause of such a failure is the dynamic change in shape of an inkcomposition near a nozzle. As a result, the inventors have found thatdroplets of the ink composition can be stably ejected from the nozzle soas to have a uniform shape as designed in such a manner that theexpansibility of the ink composition is controlled within a specificrange.

SUMMARY

An advantage of some aspects of the invention is to provide an inkcomposition having expansibility controlled within a specific range.

The invention can be accomplished in embodiments or applications below.

(Application 1)

An ink composition according to an embodiment of the invention has aviscosity of 25 mPa·s to 35 mPa·s at 20° C., wherein a, b, and c are 800or more, 7.4 to 14, and 0.16 to 0.22, respectively, when a cylindricalportion is formed by expanding the ink composition so as to have a freesurface parallel to the expanding direction of the ink composition, therate of change in width of the cylindrical portion with time is measuredin the expanding direction thereof, and the rate of change in width ofthe cylindrical portion with time is fit to a quadratic function givenby the following equation:S=−at ² −bt+c  (1)where S is the rate of change in width of the cylindrical portion and tis the time in seconds.

The ink composition can be stably ejected from an ink-ejecting head ofan ink jet recording apparatus. Thus, a high-quality image in whichprint positions are hardly displaced or which is less affected bysatellites can be provided.

(Application 2)

In Application 1, the rate of change S may be based on the width of thecylindrical portion at the beginning of expansion.

The ink composition can be stably ejected from an ink-ejecting head ofan ink jet recording apparatus.

(Application 3)

In Application 1 or 2, the time taken to reduce the width of thecylindrical portion to zero may be within 0.1 second from the beginningof expansion.

The ink composition can be quickly separated into droplets after beingejected.

(Application 4)

In any one of Applications 1 to 3, the ink composition may contain atleast one polymerizable compound and at least one photopolymerizationinitiator.

The ink composition is a type of photocurable ink composition and canprovide a high-quality image in which print positions are hardlydisplaced or which is less affected by satellites.

(Application 5)

A recording method according to an embodiment of the invention includesejecting the ink composition according to any one of Applications 1 to 4from an ink jet recording head such that the ink composition is appliedto a recording medium.

The recording method uses the ink composition, which can be stablyejected from an ink jet recording head; hence, a high-quality image inwhich print positions are hardly displaced or which is less affected bysatellites can be quickly formed on a recording medium by the recordingmethod.

(Application 6)

In Application 5, the driving frequency F of the ink jet recording headmay be 1 kHz to 200 kHz.

Since the driving frequency F of the ink jet recording head is 1 kHz to200 kHz, a high-density image can be quickly formed on a recordingmedium by the recording method.

(Application 7)

In Application 5 or 6, the ink jet recording head includes a nozzle forejecting the ink composition and the nozzle has a diameter of 1 μm to 50μm.

According to the recording method, a higher-density image can be quicklyformed on a recording medium.

(Application 8)

In any one of Applications 5 to 7, droplets of the ink compositionapplied to the recording medium may each have a volume of 0.1 pl to 20pl.

According to the recording method, a higher-density image can be quicklyformed on a recording medium.

(Application 9)

In any one of Applications 5 to 8, the ink jet recording head includes amultilayer piezoelectric element and is operated in a longitudinal mode.

According to the recording method, a high-quality image in which printpositions are hardly displaced or which is less affected by satellitescan be formed on a recording medium.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention will be described with reference to the accompanyingdrawings, wherein like numbers reference like elements.

FIGS. 1A to 1C are illustrations showing an ink composition beingexpanded.

FIG. 2 is a graph showing results obtained by fitting.

DESCRIPTION OF EXEMPLARY EMBODIMENTS

Embodiments of the invention will now be described. The embodiments arefor illustrative purposes only. The invention is not limited to theembodiments and includes various modifications made within the scope ofthe invention. All configurations described in the embodiments are notnecessarily essential elements of the invention.

1. Ink Composition

1.1. Properties of Ink Composition

An ink composition according to an embodiment of the invention has aviscosity of 25 mPa·s to 35 mPa·s at 20° C. The ink compositionpreferably has a viscosity of 10 mPa·s to 15 mPa·s at 40° C. Theviscosity of the ink composition is controlled on the basis of thecontent, molecular weight, molecular structure, and molecularinteraction of each component contained in the ink composition. When theviscosity of the ink composition is within the above range at 20° C.,the viscosity thereof can be reduced to below the above range by heatingthe ink composition to higher than 20° C. The viscosity of the inkcomposition can be readily adjusted to, for example, 10 mPa·s to 15mPa·s at 40° C. Therefore, the ink composition can be well ejected froman ink jet recording head by, for example, heating the ink jet recordinghead. The ink composition can be well ejected from the ink jet recordinghead by heating the ink composition to higher than 20° C. because theviscosity of the ink composition is less than the viscosity at 20° C.The temperature at which the ink composition is ejected from the ink jetrecording head is not limited to 40° C., which is used as a guide. Ifthe ink composition can be ejected, the temperature of the inkcomposition may be 20° C. or lower. When the viscosity of the inkcomposition is outside the range of 25 mPa·s to 35 mPa·s at 20° C., itmay be difficult to eject the ink composition with, for example, an inkjet recording apparatus. The viscosity of the ink composition can bemeasured by an ordinary method.

The ink composition is characterized in such a manner that a cylindricalportion is formed by expanding the ink composition so as to have a freesurface parallel to the expanding direction of the ink composition andthe rate of change in width of the cylindrical portion with time ismeasured in the expanding direction thereof. The ink composition iscontrolled such that a, b, and c are 800 or more, 7.4 to 14, and 0.16 to0.22, respectively, when the rate of change in width of the cylindricalportion with time is fit to a quadratic function given by the followingequation:S=−at ² −bt+c  (1)where S is the rate of change in width of the cylindrical portion and tis the time in seconds.

The term “expanding the ink composition” as used herein means that atensile displacement is applied to a droplet of the ink composition. Theterm “cylindrical portion” as used herein refers to a continuous portionof the ink composition that is formed between two clots when the inkcomposition is being separated into the two clots by expanding the inkcomposition. The term “free surface” as used herein refers to a surfacewhich is out of contact with any solid and of which the shape isprincipally determined by the action of surface tension. The continuousportion of the ink composition that is formed between the two clotsformed by expanding the ink composition corresponds to the free surfaceand therefore has a cylindrical shape or a waisted cylindrical shape(such a shape that a center portion of a cylinder is narrow than otherportions).

The width of the cylindrical portion is herein defined as the size ofthe cylindrical portion in the direction perpendicular to the expandingdirection of the cylindrical portion and corresponds to the width of thenarrowest part of the cylindrical portion when the cylindrical portionis waisted. The cylindrical portion, which corresponds to the freesurface as described above, has a cross section which is perpendicularto the expanding direction of the cylindrical portion and which is veryclose to a circular shape. Therefore, when viewed in the directionperpendicular to the expanding direction of the cylindrical portion, thewidth of the cylindrical portion can be measured in any direction. Theunit of the time t in Equation (1) is “second”. The origin of the time tis set between the point in time when the ink composition begins to beexpanded and the point in time when the ink composition is separatedinto the two clots.

The rate of change S in width is defined as the ratio of the width ofthe cylindrical portion at the moment of measurement to the width of thecylindrical portion at a specific point in time while the inkcomposition is being separated into the two clots. The rate of change Sin width is expressed in, for example, percent. The width of thecylindrical portion is preferably 100 μm to 1 cm depending on ameasuring method.

A method for measuring the width (the rate of change S) with time t canbe exemplified as follows: for example, the width of the cylindricalportion is measured using a laser beam and a detector, placed oppositethe laser beam with a sample disposed therebetween, for detecting thelaser beam while the ink composition is being expanded. The method formeasuring the width with time t is not limited to an optical method andmay be an electrical method or a method using a high-speed camera or thelike. As an example of an apparatus useful in measuring the width withtime t, a commercially available extensional viscometer can be listed.The extensional viscometer is described in detail in examples below.

Fitting the rate of change S with time t to a quadratic functioncorresponds to the determination of a quadratic function most closelyapproximated by the method of least squares for the rate of change S andtime t determined as described above. The determined quadratic functionis given by the equation S=−at²−bt+c and the values of a, b, and c aredetermined.

Upon fitting, the origin (0) of the time t is set to the point in timewhen the width of the cylindrical portion is reduced sufficiently toallow the width of the cylindrical portion to meet specific conditions,whereby the accuracy of fitting the quadratic function can be increased.This is because the width of the cylindrical portion becomes less than aspecific value by expanding the ink composition and therefore a flow ofthe ink composition in the cylindrical portion becomes one-dimensional(an expansion fluid state).

As a result of fitting, the time ts (s) can be determined from thex-intercept (a width of 0) of the quadratic function. Therefore, forexample, the time ts from when expanding is started or the flow of theink composition in the cylindrical portion becomes one-dimensional (anexpansion fluid state) to when the width is reduced to zero can bedetermined. The time is of the ink composition is preferably 0.1 s orless.

The ink composition is controlled on the basis of the content, molecularweight, molecular structure, and molecular interaction of each componentcontained in the ink composition and the zeta potential of particles ofa colorant or the like, if contained, such that a, b, and c in Equation(1) are 800 or more, 7.4 to 14, and 0.16 to 0.22, respectively. When a,b, and c therein are outside the above ranges, for example, the rate atwhich the width of the cylindrical portion is reduced is insufficient.Hence, the rate at which the two clots of the ink composition areseparated is likely to be small or third droplets (mists) are likely tobe formed during separation.

Since the rate at which the width of the cylindrical portion of the inkcomposition is reduced is sufficiently small, the ink composition can bestably ejected from ink-ejecting heads of ink jet recording apparatuses.Thus, high-quality images in which print positions are hardly displacedor which are less affected by satellites can be provided.

1.2. Components of Ink Composition

Components of the ink composition are not particularly limited. The inkcomposition may contain, for example, polymerizable compound and aphotopolymerization initiator at least.

1.2.1. Polymerizable Compound

The ink composition may contain the polymerizable compound. Examples ofthe polymerizable compound include cationically polymerizable compoundsand radically polymerizable compounds. The polymerizable compound maycontain a cationically polymerizable functional group and a radicallypolymerizable functional group. In this embodiment, the polymerizablecompound characterized in that the polymerizable compound is polymerizedand cured by at least one of cationic polymerization and radicalpolymerization. The polymerizable compound can be used in the form of amonomer, an oligomer, a linear polymer, or dendritic polymer.

The radically polymerizable functional group, which is contained in thepolymerizable compound usable in the ink composition, may be afunctional group having a double bond. Examples of the radicallypolymerizable functional group include a (meth)acrylic group; a(meth)acrylamide group; a vinyl group; aromatic vinyl groups; allylgroups; N-vinyl groups; vinyl ester groups such as groups having a vinylacetate moiety, a vinyl propionate moiety, or a vinyl versatate moiety;allyl ester groups such as groups having an allyl acetate moiety;halogenated vinyl groups such as groups having a vinylidene chloridemoiety or a vinyl chloride moiety; vinyl ether groups such as groupshaving a methyl vinyl ether moiety, a butyl vinyl ether moiety, a hexylvinyl ether moiety, a methoxy vinyl ether moiety, a 2-ethylhexyl vinylether moiety, a methoxy ethyl vinyl ether moiety, a cyclohexyl vinylether moiety, or a chloroethyl vinyl ether moiety; vinyl cyanide groupssuch as groups having a (meth)acrylonitrile moiety); and alkenyl groups.The term “(meth)acrylate” as used herein refers to one or both of“acrylate” and “methacrylate”. The term “(meth)acrylic” as used hereinrefers to one or both of “acrylic” and “methacrylic”.

Among those exemplified above, a functional group having anethylenically unsaturated double bond is highly polymerizable andtherefore is more preferred in order to improve the curing rate and thecurability of the ink composition deposited on a recording surface. Sucha group is unlikely to be susceptible to oxygen inhibition and thereforeis curable with relatively low energy, which is more preferred. Examplesof the functional group having such an ethylenically unsaturated doublebond include a vinyl group and allyl groups. The polymerizable compoundpreferably contains a plurality of radically polymerizable functionalgroups in view of reaction rate and curability.

Examples of the polymerizable compound includemonofunctional(meth)acrylates; polyfunctional(meth)acrylates;(meth)acrylic amides; vinyl aromatics; aryl compounds; N-vinylcompounds; vinyl eaters such as vinyl acetate, vinyl propionate, andvinyl versatate; aryl esters such as aryl acetate; halogen-containingmonomers such as vinylidene chloride and vinyl chloride; vinyl etherssuch as methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether,methoxy vinyl ether, 2-ethylhexyl vinyl ether, methoxyethyl vinyl ether,cyclohexyl vinyl ether, and chloroethyl vinyl ether; vinyl cyanate suchas (meth)acrylonitrile; and olefins such as ethylene and propylene.

Examples of the monofunctional(meth)acrylates includehexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate,tert-octyl(meth)acrylate, isoamyl(meth)acrylate, decyl(meth)acrylate,isodecyl(meth)acrylate, stearyl(meth)acrylate, isostearyl(meth)acrylate,cyclohexyl(meth)acrylate, 4-n-butylcyclohexyl(meth)acrylate,bornyl(meth)acrylate, isobornyl(meth)acrylate, benzyl(meth)acrylate,2-ethylhexyl diglycol(meth)acrylate, butoxy(meth)acrylate,2-chloroethyl(meth)acrylate, 4-bromobutyl(meth)acrylate,cyanoethyl(meth)acrylate, benzyl(meth)acrylate,butoxymethyl(meth)acrylate, 3-methoxybutyl(meth)acrylate,alkoxymethyl(meth)acrylate, alkoxyethyl(meth)acrylate,2-(2-methoxyethoxyl)ethyl(meth)acrylate,2-(2-butoxyethoxyl)ethyl(meth)acrylate,2,2,2-trifluoroethyl(meth)acrylate,1H,1H,2H,2H-perfluorodecyl(meth)acrylate, 4-butylphenyl(meth)acrylate,phenyl(meth)acrylate, trimethylphenyl(meth)acrylate,4-chlorophenyl(meth)acrylate, phenoxymethyl(meth)acrylate,phenoxyethyl(meth)acrylate, glycidyl(meth)acrylate,glycidyloxybutyl(meth)acrylate, glycidyloxyethyl(meth)acrylate,glycidyloxypropyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate,hydroxyalkyl(meth)acrylates, 2-hydroxyethyl(meth)acrylate,3-hydroxypropyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate,2-hydroxybutyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate,dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate,dimethylaminopropyl(meth)acrylate, diethylaminopropyl(meth)acrylate,trimethoxysilylpropyl(meth)acrylate, dicyclopentenyl(meth)acrylate,dicyclopentenyloxy(meth)acrylate, trimethoxylsilylpropyl(meth)acrylate,trimethylsilylpropyl(meth)acrylate, polyethylene oxide monomethylether(meth)acrylate, oligoethylene oxide monomethyl ether(meth)acrylate,polyethylene oxide(meth)acrylate, oligoethylene oxide(meth)acrylate,oligoethylene oxide monoalkyl ether(meth)acrylates, polyethylene oxidemonoalkyl ether(meth)acrylates, dipropylene glycol(meth)acrylate,polypropylene oxide monoalkyl ether(meth)acrylates, oligopropylene oxidemonoalkyl ether(meth)acrylates, 2-methacryloyloxylsuccinic acid,2-methacryloyloxy]hexahydrophthalic acid,2-methacryloyloxyethyl-2-hydroxypropyl phthalate, butoxydiethyleneglycol(meth)acrylate, trifluoroethyl(meth)acrylate,perfluorooctylethyl(meth)acrylate,2-hydroxy-3-phenoxypropyl(meth)acrylate, EO-modifiedphenol(meth)acrylate, EO-modified cresol(meth)acrylate, EO-modifiednonylphenol(meth)acrylate, PO-modified nonylphenol(meth)acrylate, andEO-modified 2-ethylhexyl(meth)acrylate.

Examples of the polyfunctional(meth)acrylates includebifunctional(meth)acrylates such as 1,6-hexanediol di(meth)acrylate,1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate,dipropylene glycol di(meth)acrylate (DPGD(M)A), tripropylene glycoldi(meth)acrylate (TPGD(M)A), 2,4-dimethyl-1,5-pentanedioldi(meth)acrylate, butylethylpropanediol di(meth)acrylate, ethoxylatedcyclohexane methanol di(meth)acrylate, triethylene glycoldi(meth)acrylate (TEGD(M)A), polyethylene glycol di(meth)acrylate,oligoethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate,2-ethyl-2-butyl-butanediol di(meth)acrylate, neopentyl hydroxypivalateglycol di(meth)acrylate, dimethylol tricyclodecane di(meth)acrylate,EO-modified bisphenol-A di(meth)acrylate, bisphenol-F polyethoxydi(meth)acrylate, polypropylene glycol di(meth)acrylate, oligopropyleneglycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate,2-ethyl-2-butylpropanediol di(meth)acrylate, 1,9-nonanedioldi(meth)acrylate, propoxylated ethoxylated bisphenol-A di(meth)acrylate,and tricyclodecane di(meth)acrylate.

Other examples of the polyfunctional(meth)acrylates includetrifunctional(meth)acrylates such as trimethylolpropanetri(meth)acrylate, trimethylolethane tri(meth)acrylate,alkyleneoxide-modified tri(meth)acrylate of trimethylolpropane,pentaerithrytol tri(meth)acrylate, dipentaerithrytol tri(meth)acrylate,trimethylolpropane tri(meth)acryloyloxypropyl) ether, isocyanuricalkyleneoxide-modified tri(meth)acrylate, dipentaerithrytol propionatetri(meth)acrylate, tri((meth)acryloyloxyethyl) isocyanulate,hydroxypivalaldehyde-modified dimethylolpropane tri(meth)acrylate,sorbitol tri(meth)acrylate, propoxylated trimethylolpropanetri(meth)acrylate, and ethoxylated glycerin triacrylate;tetrafunctional(meth)acrylates such as pentaerithrytoltetra(meth)acrylate, sorbitol tetra(meth)acrylate, ditrimethylolpropanetetra(meth)acrylate, dipentaerithrytol propionate tetra(meth)acrylate,and ethoxylated pentaerithrytol tetra(meth)acrylate;pentafunctional(meth)acrylates such as sorbitol penta(meth)acrylate anddipentaerithrytol penta(meth)acrylate; and hexafunctional(meth)acrylatessuch as dipentaerithrytol hexa(meth)acrylate, sorbitolhexa(meth)acrylate, alkylene oxide-modified hexa(meth)acrylates ofphosphazenes, and captolactone-modified dipentaerithrytolhexa(meth)acrylate.

Other examples of the polyfunctional(meth)acrylates include compoundscontaining a plurality of (meth)acryloyl groups, that is, linearpolymers each containing a plurality of (meth)acryloyl groups anddendritic polymers each containing a plurality of (meth)acryloyl groups.An example of the dendritic polymers containing such (meth)acryloylgroups is a compound, Biscoat #1000, available from Osaka OrganicChemical Industry Ltd. This compound is a hyper branched polymer,synthesized from pentaerithrytol, having branched groups. This compoundcontains acryloyl groups densely arranged at the surface of its moleculeand therefore can be successfully used as the polymerizable compound.

Examples of the (meth)acrylic amides include (meth)acrylamide,N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide,N-propyl(meth)acrylamide, N-n-butyl(meth)acrylamide,N-t-butyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide,N-isopropyl(meth)acrylamide, N-methylol(meth)acrylamide,N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, and(meth)acryloyl morpholine.

Examples of the vinyl aromatics include styrene, methylstyrene,trimethystyrene, ethylstyrene, isopropylstyrene, chloromethyl styrene,methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene,bromostyrene, methyl vinylbenzoate, 3-methylstyrene, 4-methylstyrene,3-ethylstyrene, 4-ethylstyrene, 3-propylstyrene, 4-propylstyrene,3-butylstyrene, 4-butylstyrene, 3-hexylstyrene, 4-hexylstyrene,3-octylstyrene, 4-octylstyrene, 3-(2-ethylhexyl)styrene,4-(2-ethylhexyl)styrene, allylstyrene, isopropenylstyrene,butenylstyrene, octenylstyrene, 4-t-butoxycarbonylstyrene,4-methoxystyrene, and 4-t-butoxystyrene.

The aryl compounds contain a 2-propenyl (—CH₂CH═CH₂) group. The2-propenyl is also referred to as an allyl group, which is a trivialname according to the IUPAC nomenclature system. Examples of the arylcompounds include ethylene glycol monoallyl ether, diethylene glycolmonoallyl ether, allyl glycol, trimethylol propane diallyl ether,trimethylol propane monoallyl ether, pentaerythritol triallyl ether,allyl glycidyl ether, glycerin monoallyl ether, hydroxybutyl vinylether, and allyl group-containing polyoxyalkylene compounds availableunder a trade name of UNIOX, UNILUBE, POLYCERIN, or UNISAFE from NOFCorporation.

The N-vinyl compounds have a structure (>N—CH═CH₂) in which a vinylgroup is bonded to nitrogen. The N-vinyl compounds are radicallypolymerizable. Examples of the N-vinyl compounds includeN-vinylformamide, N-vinylcarbazole, N-vinylindole, N-vinylpyrrole,N-vinylacetamide, N-vinylpyrrolidone, N-vinylcaprolactam, andderivatives thereof. In particular, N-vinylformamide is preferred.N-vinylformamide is available from, for example, Arakawa Kagaku KogyoCo., Ltd.

Examples of the cationically polymerizable functional group, which iscontained in the polymerizable compound usable in the ink composition,include functional groups having an epoxy ring such as an aromatic epoxygroup or an alicyclic epoxy group, functional groups having an oxetanering, functional groups having an oxolane ring, functional groups havinga dioxolane ring, and functional groups having a vinyl ether moiety. Thearomatic and alicyclic epoxy groups are preferred because these groupshave excellent curing rates. In particular, the alicyclic epoxy group ispreferred. The polymerizable compound preferably contains a plurality ofcationically polymerizable functional groups in view of reaction rateand curability.

Examples of the cationically polymerizable compounds include epoxycompounds, vinyl ether compounds, and oxetane compounds. SpecificExamples of the cationically polymerizable compounds include oxetaneacrylate, oxetane methacrylate, 1,3-dioxolane(meth)acrylate, and(meth)acryl-modified epoxy compounds. Compounds having oxetane rings aredescribed in paragraphs [0021] to [0084] of JP-A-2003-341217 in detailand can be used herein.

The content of the polymerizable compound in the ink composition ispreferably 5% to 95%, more preferably 7% to 90%, and further morepreferably 10% to 80% on a mass basis.

1.2.2. Photopolymerization Initiator

The ink composition may contain the photopolymerization initiator asdescribed above. The photopolymerization initiator can produce activespecies for the polymerization of the polymerizable compound when thephotopolymerization initiator absorbs light.

Any photopolymerization initiators, capable of producing photoradicals,known to those skilled in the art can be used herein without limitation.Examples of the photopolymerization initiator include various initiatorsdescribed in Bruce M. Monroe et al., Chemical Review, 93, 435 (1993); R.S. Davidson, Journal of Photochemistry and biology A: Chemistry, 73, 81(1993); J. P. Faussier, “Photoinitiated Polymerization—Theory andApplications”: Rapra Review vol. 9, Report, Rapra Technology (1998); andM. Tsunooka et al., Prog. Polym. Sci., 21, 1 (1996). Other examples ofthe photopolymerization initiator include various compounds used forchemically-amplified photoresists or photocationic polymerization asdescribed in The Japanese Research Association for Organic ElectronicsMaterials, Organic Materials for Imaging, pp. 187-192, 1993, Bun-ShinPublishing. Other examples of the photopolymerization initiator includecompounds undergoing oxidative or reductive bond cleavage through theinteraction with a sensitizing dye in an electronically excited state asdescribed in F. D. Saeva, Topics in Current Chemistry, 156, 59 (1990);G. G. Maslak, Topics in Current Chemistry, 168, 1 (1993); H. B. Shusteret al., JACS, 112, 6329 (1990); and I. D. F. Eaton et al., JACS, 102,3298 (1980).

Preferred examples of the photopolymerization initiator include (a)aromatic ketones, (b) aromatic onium salts, (c) organic peroxides, (d)hexaarylbiimidazole compounds, (e) ketoxime esters, (f) borates, (g)azinium compounds, (h) metallocene compounds, (i) active esters, (j)carbon-halogen bond-containing compounds, and (k) acylphosphine oxides.

(a) Preferred examples of the aromatic ketones includeα-thiobenzophenone compounds, benzoin ethers, α-substituted benzoincompounds, benzoin derivatives, aroylphosphonates,dialkoxybenzophenones, benzoin ethers, α-aminobenzophenones,p-di(dimethylaminobenzoyl)benzene, thio-substituted aromatic ketones,acylphosphine sulfide, acylphosphine, thioxanthones, and coumarins.

(b) Examples of the aromatic onium salts include aromatic onium salts ofelements of the V, VI and VII groups of the periodic table, that is,aromatic onium salts of N, P, As, Sb, Bi, O, S, Se, Te, and I. Preferredexamples of the aromatic onium salts include sulfonium salts, diazoniumsalts such as benzodiazoniums that may have substituents, diazonium saltresins such as diazodiphenylamine formaldehyde resins, andN-alkoxypyridinium salts such as 1-methoxy-4-phenylpyridiniumtetrafluoroborate.

(c) Examples of the organic peroxides include most of organic compoundshaving one or more oxygen-oxygen bonds. Preferred examples of theorganic peroxides include peroxide esters such as3,3′,4,4′-tetra-(t-butylperoxycarbonyl)benzophenone,3,3′,4,4′-tetra-(t-amylperoxycarbonyl)benzophenone,3,3′,4,4′-tetra-(t-hexylperoxycarbonyl)benzophenone,3,3′,4,4′-tetra-(t-octylperoxycarbonyl)benzophenone,3,3′,4,4′-tetra-(cumylperoxycarbonyl)benzophenone,3,3′,4,4′-tetra-(p-isopropylperoxycarbonyl)benzophenone, anddi-t-butyldiperoxyisophthalate.

(d) Examples of the hexaarylbiimidazole compounds include2,2′-bis(o-chlorophenyl)-4,4′,5,5′-tetraphenylbiimidazole,2,2′-bis(o-bromophenyl)-4,4′,5,5′-tetraphenylbiimidazole,2,2′-bis(o,p-dichlorophenyl)-4,4′,5,5′-tetraphenylbiimidazole,2,2′-bis(o-chlorophenyl)-4,4′,5,5′-tetra(m-methoxyphenyl)biimidazole,2,2′-bis(o,o′-dichlorophenyl)-4,4′,5,5′-tetraphenylbiimidazole,2,2′-bis(o-nitrophenyl)-4,4′,5,5′-tetraphenylbiimidazole,2,2′-bis(o-methylphenyl)-4,4′,5,5′-tetraphenylbiimidazole, and2,2′-bis(o-trifluorophenyl)-4,4′,5,5′-tetraphenylbiimidazole.

(e) Examples of the ketoxime esters include3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one,3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one,2-acetoxyimino-1-phenylpropane-1-one,2-benzoyloxyimino-1-phenylpropane-1-one, 3-p-toluenesulfonyloxyiminobutane-2-one, and2-ethoxycarbonyloxyimino-1-phenylpropane-1-one.

(f) Examples of the borates, which are examples of thephotopolymerization initiator used herein, include compounds describedin U.S. Pat. Nos. 3,567,453 and 4,343,891 and European Patent Nos.109,772 and 109,773. (g) Examples of the azinium compounds, which areexamples of the photopolymerization initiator used herein, include N—Obond-containing compounds disclosed in JP-A Nos. 63-138345, 63-142345,63-142346, and 63-143537.

(h) Examples of the metallocene compounds, which are examples of thephotopolymerization initiator used herein, include titanocene compoundsdisclosed in JP-A Nos. 59-152396, 61-151197, 63-41484, 2-249, and 2-4705and iron-arene complexes disclosed in JP-A Nos. 1-304453 and 1-152109.Examples of the titanocene compounds includedicyclopentadienyl-Ti-dichloride, dicyclopentadienyl-Ti-bis-phenyl,dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl,dicyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl,dicyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl-1-yl,dicyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl,dicyclopentadienyl-Ti-bis-2,4,-difluorophenyl-1-yl,dimethylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl,dimethylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl,bis(cyclopentadienyl)-bis(2,6-difluoro-3-(pyri-1-yl)phenyl)titanium,bis(cyclopentadienyl)bis[2,6-difluoro-3-(methylsulfoneamide)phenyl]titanium,andbis(cyclopentadienyl)bis[2,6-difluoro-3-(N-butylbiaroyl-amino)phenyl]titanium.

(i) Examples of the active esters include nitrobenzyl esters andiminosulfonates.

(j) Preferred examples of the carbon-halogen bond-containing compoundsinclude compounds available under a trade name of Vicure 10 or Vicure 30from Stauffer Chemical Co.; compounds available under a trade name ofIrgacure 127, Irgacure 184, Irgacure 500, Irgacure 651, Irgacure 2959,Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 754, Irgacure 1700,Irgacure 1800, Irgacure 1850, Irgacure 819, OXE 01, Darocure 1173, orITX from Ciba Specialty Chemicals Inc.; a compound available under atrade name of Quantacure CTX from Aceto Chemical Co., Inc.; a compoundavailable under a trade name of Kayacure DETX-S from Nippon Kayaku Co.,Ltd.; and a compound available under a trade name of ESACURE KIP 150from Lamberti.

(k) Preferred examples of the acylphosphine oxides includediphenyl(2,4,5-trimethylbenzoyl)phosphine oxide and a compound availableunder a trade name of Darocure TPO from Ciba Specialty Chemicals Inc.

When the ink composition contains the photopolymerization initiator, thecontent of the photopolymerization initiator in the ink composition is1% to 20% and more preferably 3% to 15% on a mass basis. When thecontent thereof is within the above range, the curability of the inkcomposition can be ensured without reducing the mechanical strength ofthe cured ink composition. The photopolymerization initiator may beselected from those sensitive to light applied thereto.

1.2.3. Other Components

1.2.3.1. Colorant and Dispersant

The ink composition may contain a colorant and a dispersant.

Examples of the colorant include pigments and dyes. Any colorants foruse in ordinary inks can be used herein without limitation.

Examples of a dye that may be contained in the ink composition includevarious dyes, such as direct dyes, acid dyes, food dyes, basic dyes,reactive dyes, dispersed dyes, vat dyes, soluble vat dyes, and reactivedispersion dyes, usually used for ink jet recording.

Examples of a pigment that may be contained in the ink compositioninclude inorganic pigments and organic pigments.

Examples of the inorganic pigments include titanium oxide, iron oxide,and carbon black produced by a known process such as a contact process,a furnace process, or a thermal process. Examples of the organicpigments include azo pigments such as azo lakes, insoluble azo pigments,condensed azo pigments, and chelate azo pigments; polycyclic pigmentssuch as phthalocyanine pigments, perylene pigments, perinone pigments,anthraquinone pigments, quinacridone pigments, dioxazine pigments,thioindigo pigments, isoindolinone pigments, and quinophthalonepigments; dye chelates such as basic dye chelates and acid dye chelates;nitro pigments; nitroso pigments; and aniline black.

Examples of the pigments include black pigments, yellow pigments,magenta pigments, cyan pigments, and white pigments. Examples of theblack pigments include C. I. Pigment Black 7; Carbon Black No. 2300, No.900, MCF88, No. 33, No. 40, No. 45, No. 52, MA7, MA8, MA100, and No.2200B available from Mitsubishi Kasei Corporation; Raven 5750, Raven5250, Raven 5000, Raven 3500, Raven 1255, and Raven 700 available fromColombia; Regal 400R, Regal 330R, Regal 660R, Mogul L, Mogul 700,Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100,Monarch 1300, and Monarch 1400 available from Cabot; and Color BlackFW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color BlackFW200, Color Black 5150, Color Black 5160, Color Black 5170, Printex 35,Printex U, Printex V, Printex 140U, Special Black 6, Special Black 5,Special Black 4A, and Special Black 4 available from Degussa.

Examples of the yellow pigments include C. I. Pigment Yellow 1, 2, 3,12, 13, 14, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 109, 110, 114, 120,128, 129, 138, 150, 151, 154, 155, 180, 185, and 213 and CHROMOPHTALYELLOW LA2 available from Ciba Specialty Chemicals Inc.

Examples of the magenta pigments include C. I. Pigment Red 5, 7, 12,48(Ca), 48(Mn), 57(Ca), 57:1, 112, 122, 123, 168, 184, 202, 209, C. I.Pigment Violet 19, and Hostaperm Pink E02 available from Clariant(Japan) K.K.

Examples of the cyan pigments include C. I. Pigment Blue 1, 2, 3, 15:3,15:4, 60, 16, 22, and TGR-SD available from DIC Corporation.

Examples of the white pigments include C. I. Pigment White 6.

The ink composition may contain a plurality of colorants. The inkcomposition may contain, for example, four basic color colorants: ayellow colorant, a magenta colorant, a cyan colorant, and a blackcolorant. The ink composition may further contain colorants each havinga color darker or lighter than that of a corresponding one of the fourbasic color colorants. That is, the ink composition may further containa light magenta colorant, a red colorant, a light cyan colorant, a bluecolorant, a gray colorant, and a matte black colorant in addition to thefour basic color colorants.

When the ink composition contains a pigment, the pigment preferably hasan average particle size of about 10 nm to 200 nm and more preferablyabout 50 nm to 150 nm. When the ink composition contains a colorant, thecontent of the colorant in the ink composition is preferably about 0.1%to 25% and more preferably about 0.5% to 15% on a mass basis.

When the ink composition contains the pigment, a pigment dispersionprepared by dispersing the pigment in a medium with a dispersant or asurfactant can be used to produce the ink composition. When the inkcomposition contains the pigment, the dispersant or the surfactant maybe contained in the ink composition in addition to the pigment. Apreferred example of the dispersant may be, for example, a polymericdispersant usually used to prepare pigment dispersions.

The dispersant may be any one for use in ordinary ink. The dispersant ispreferably one that acts effectively when an organic solvent used has asolubility parameter of 8 to 11. Commercially available examples of thedispersant include polyester compounds, such as Hinoacto KF1-M, T-6000,T-7000, T-8000, T-8350P, and T-8000 EL, available from Takefu FineChemicals Co., Ltd.; dispersants, such as Solsperse 13940, 20000, 24000,32000, 32500, 33500, 34000, and 35200, available from The LubrizolCorporation; dispersants such as Disperbyk-161, 162, 163, 164, 166, 180,190, 191, and 192 available from Byk Chemie; dispersants such as FlowlenDOPA-17, DOPA-22, DOPA-33, and G-700 available from Kyoeisha ChemicalCo., Ltd.; dispersants such as Ajisper PB821 and PB711 available fromAjinomoto Co., Inc.; and dispersants such as LP4010, LP4050, LP4055,POLYMER 400, POLYMER 401, POLYMER 402, POLYMER 403, POLYMER 450, POLYMER451, and POLYMER 453 available from EFKA Chemicals. These dispersantsmay be used alone or in combination.

When the ink composition contains the dispersant, the content of thedispersant in the ink composition is preferably 5% to 200% and morepreferably 30% to 120% by mass of the content of the colorant(particularly the pigment) in the ink composition and may beappropriately selected depending on the colorant to be dispersed.

1.2.3.2. Additives

The ink composition may contain a polymerization accelerator. Examplesof the polymerization accelerator include, but are not limited to,Darocur EHA and EDB available from Ciba Specialty Chemicals Inc.

The ink composition may contain a thermoradical polymerizationinhibitor. This allows the ink composition to have increased storagestability. Examples of the thermoradical polymerization inhibitorinclude methyl ether hydroquinone (MEHQ) available from Kanto ChemicalCo., Inc. and polymerization inhibitors, such as Irgastab UV-10 andUV-22, available from Ciba Specialty Chemicals Inc.

The ink composition may further contain a surfactant. The surfactant maybe anionic, cationic, amphoteric, or nonionic. Examples of thesurfactant include silicone surfactants such as polyester-modifiedsilicones and ether-modified silicones, polyether-modifieddimethylsiloxanes, and polyester-modified polydimethylsiloxanes.Specific examples of the surfactant include surfactants, such asBYK-347, BYK-348, BYK-UV3500, BYK-UV3510, BYK-UV3530, and BYK-UV3570,available from Byk Chemie Japan K.K. and a surfactant, such as UV-3500,available from Ciba Specialty Chemicals Inc. When the ink compositioncontains the surfactant, the content of the surfactant in the inkcomposition is preferably 0.5% to 4.0% by mass.

The ink composition may further contain a known component usable forordinary inks. Examples of such a component include antioxidants,humectants, infiltration solvents, pH adjustors, antiseptics, antimildewagents, and adhesion promoters.

Examples of the antioxidants include BHA (2,3-dibutyl-4-oxyanisole) andBHT (2,6-di-t-butyl-p-cresol). When the ink composition contains anantioxidant, the content of the antioxidant in the ink composition ispreferably 0.01% to 3.0% by mass. The presence of an adhesion promoterin the ink composition allows the ink composition to have increasedadhesion to recording media. Preferred examples of the adhesion promoterinclude amino acrylates, such as EBECRYL 7100 and 8402, available fromDAICEL-CYTEC Co., Ltd.

The ink composition may further contain an ultraviolet absorber; aleveling agent; a matting agent; and a material, such as a polyesterresin, a polyurethane resin, a vinyl resin, an acrylic resin, a rubberresin, or wax, for adjusting film properties as required. A usefulexample of the ultraviolet absorber is a benzophenone or benzotriazolecompound. The presence of the ultraviolet absorber in the inkcomposition allows records to have increased light resistance. When theink composition contains the ultraviolet absorber, the content of theultraviolet absorber in the ink composition is preferably 0.01% to 0.5%by mass.

When the ink composition contains the above exemplified components, theink composition is controlled on the basis of the content, molecularweight, molecular structure, and molecular interaction of each componentand the zeta potential of particles of a colorant or the like, ifcontained, such that a, b, and c in Equation (1) are 800 or more, 7.4 to14, and 0.16 to 0.22, respectively.

1.3. Light

When the ink composition contains the polymerizable compound and thephotopolymerization initiator, examples of light applied to the inkcomposition include 200-400 nm ultraviolet rays, visible light, farultraviolet rays, g-line, h-line, i-line, KrF excimer laser beams, ArFexcimer laser beams, electromagnetic waves such as X-rays, and particlebeams such as electron beams and alpha rays. A source of light appliedthereto is not particularly limited.

In the case of applying an ultraviolet ray to the ink composition, thedose of the ultraviolet ray is preferably 10 mJ/cm² to 20,000 10 mJ/cm²and more preferably 50 mJ/cm² to 15,000 10 mJ/cm². When the dose of theultraviolet ray is within this range, the polymerizable compound can besufficiently cured.

Examples of a lamp used to apply the ultraviolet ray to the inkcomposition include metal halide lamps, xenon lamps, carbon arc lamps,chemical lamps, low-pressure mercury lamps, and high-pressure mercurylamps. In particular, the ultraviolet ray can be applied to the inkcomposition using, for example, a commercially available lamp such as anH lamp, D lamp, or V lamp available from Fusion System Corporation orSubZero 055 available from Integration Technology, Inc. Alternatively,the following device can be used to apply the ultraviolet ray to the inkcomposition: an ultraviolet light-emitting semiconductor device such asan ultraviolet light-emitting diode (UVLED) or an ultravioletlight-emitting semiconductor laser.

In the case of using, for example, an ink jet recording apparatus, theink composition may be irradiated with light in the ink jet recordingapparatus. Alternatively, after dots are formed with an ink jetrecording apparatus including no irradiation system using the inkcomposition, the dots may be irradiated with light with an irradiationsystem.

1.4. Recording Method

A recording method according to an embodiment of the invention includesapplying the ink composition to a recording medium by ejecting the inkcomposition from an ink jet recording head. In this embodiment, it isexemplified that the ink composition is ejected toward the recordingmedium using an ink jet recording apparatus and dots are formed byapplying the ink composition to the recording medium.

1.4.1. Ink Jet Recording Head

Examples of a recording process using the ink jet recording apparatusinclude a process (electrostatic attraction process) in which recordingis performed in such a manner that a strong electric field is appliedbetween a nozzle and an accelerating electrode disposed in front of thenozzle, droplets of ink are continuously ejected from the nozzle, andprinting information signals are applied to deflection electrodes whilethe ink droplets are passing between the deflection electrodes or insuch a manner that the ink droplets are ejected in accordance with theprinting information signals without deflecting the ink droplets, aprocess in which ink droplets are ejected in such a manner that an inksolution is pressurized with a micro-pump and a nozzle is mechanicallyvibrated with a quartz oscillator, a process (piezoelectric process) inwhich ink droplets are ejected for recording in such a manner that apressure and a printing information signal are applied to an inksolution with a piezoelectric element at the same time, and a process(thermal jet process) in which ink droplets are ejected for recording insuch a manner that an ink solution is heated and bubbled with amicro-electrode in accordance with an printing information signal.

The piezoelectric process can be categorized into a process using a thinfilm-type ink jet recording head and a process using a multilayer inkjet recording head. The thin film-type ink jet recording head includes apiezoelectric actuator, which is of a so-called unimorph type, andejects an ink composition from a nozzle by the displacement of thepiezoelectric actuator. The multilayer ink jet recording head includes amultilayer piezoelectric element and ejects an ink composition from anozzle in such a manner that the wall of a pressure chambercommunicating with the nozzle is pressed by driving the multilayerpiezoelectric element in a d₃₁ mode. The multilayer ink jet recordinghead is also referred to as a longitudinal-mode ink jet recording headbecause the multilayer piezoelectric element presses the wall of thepressure chamber. Both the thin film-type ink jet recording head and themultilayer ink jet recording head can eject the ink composition. Themultilayer ink jet recording head, that is, the longitudinal-mode inkjet recording head, can eject the ink composition with a relativelylarge force and therefore can quickly form a high-quality image in whichprint positions are hardly displaced or which is less affected bysatellites and the like. The thin film-type ink jet recording head canbe operated at a relatively high speed and therefore can quickly form ahigh-definition, high-quality image in which print positions are hardlydisplaced or which is further less affected by satellites and the like.

In the recording method, the driving frequency F of an ink jet recordinghead used in each of the electrostatic attraction process, thepiezoelectric process, and the thermal jet process is preferably 1 kHzto 200 kHz. The driving frequency F of the ink jet recording headcorresponds to the frequency of the voltage applied to the ink jetrecording head. The voltage applied thereto has a simple sinusoidalwaveform or a waveform consisting of a plurality of superimposed wavesin some cases. Therefore, the driving frequency F is herein defined asthe reciprocal of the shortest time taken to eject two droplets of theink composition from one nozzle. In other words, the driving frequency Fcorresponds to the number of droplets ejectable from one nozzle persecond. When the driving frequency F is 1 kHz to 200 kHz, a high-qualityimage in which print positions are hardly displaced or which is lessaffected by satellites and the like can be quickly formed on a recordingmedium.

In the recording method, the ink jet recording head used in each of theelectrostatic attraction process, the piezoelectric process, and thethermal jet process preferably includes a nozzle with a diameter of 1 μmto 50 μm. This allows a high-definition image on a recording medium. Inthe ink jet recording head used in each of the electrostatic attractionprocess, the piezoelectric process, and the thermal jet process,droplets of the ink composition preferably each have a volume of 0.1 plto 20 pl. This allows a high-definition image on a recording medium.

The ink jet recording apparatus used in this embodiment can beexemplified as one including the ink jet recording head, a body, a tray,a head drive, a carriage, and the like. The ink jet recording head mayinclude cartridges containing at least four differently colored inkssuch as a cyan ink, a magenta ink, a yellow ink, and a black ink so asto be capable of performing full-color printing. In this embodiment, atleast one of the cartridges is filled with the ink composition. Theother cartridges may be filled with ordinary inks. The ink jet recordingapparatus includes a dedicated control board and the like and thereforecan control the timing of ink ejection of the ink jet recording head andcontrol the scanning of the head drive.

The ink jet recording apparatus preferably includes a unit capable oflight irradiation for the purpose of curing the ink composition, whichcontains the polymerizable compound and the photopolymerizationinitiator. Such a unit can be exemplified as, for example, anultraviolet irradiation device, which is mounted on a side surface ofthe carriage in the ink jet recording apparatus.

1.4.2. Recording Medium

A recording medium used in this embodiment is not particularly limitedand can be coated with droplets of the ink composition with the ink jetrecording apparatus. Examples of the recording medium include absorptiverecording media such as paper, porous sheets, and cloth andnon-absorptive recording media such as metal, glass, and plastic. Thechoice of the absorptive or non-absorptive recording media depends oncomponents contained in the ink composition. The recording medium may bea colorless transparent medium, a translucent medium, a coloredtransparent medium, a colored opaque medium, a colorless opaque medium,or the like.

The recording medium may be glossy, matte, or dull. Examples of therecording medium include treated paper sheets such as coated papersheets, art paper sheets, and cast-coated paper sheets and plastic filmssuch as polyvinyl chloride sheets and PET films. Commercially availableexamples of the recording medium include pearl-coated paper sheetsavailable from Mitsubishi Paper Mills Ltd., Aurora Coat paper (coatedprinting paper) sheets available from Nippon Paper Industries Co., Ltd.,glossy polyvinyl chloride sheets available under a trade name ofSP-SG-1270C from Roland DG Corporation, and PET films available under atrade name of XEROX FILM (frameless) from Fuji Xerox Co., Ltd.

2. Examples and Comparative Examples

The invention is further described below in detail with reference toexamples and comparative examples, which do not limit the scope of theinvention.

2.1. Ink Compositions

Ink compositions were prepared in Examples 1 to 8 and ComparativeExamples 1 to 6. The composition and components of each ink compositionwere summarized in Table 1.

TABLE 1 Examples Comparative Examples Components (parts by mass) 1 2 3 45 6 7 8 1 2 3 4 5 6 Monofunctional V#192 15 15 30 15 30 15 15 15 37 3730 37 37 30 polymerizable FA-512AS — — — — 2 — 2 2 20 18 20 15 15 25compounds FA-511AS — — — — 2 — 2 2 10 8 10 5 5 15 Vinyl 15 15 10 15 1015 15 15 — — 10 — 2 10 caprolactam Bifunctional DPGDA 25 20 15 20 15 2023 23 — 2 — 5 5 5 polymerizable TPGDA 25 25 15 25 15 25 23 23 — 2 — 5 55 compounds TEGDA — — — — — — — 2 8 8 — 8 8 — A-DCP — — 9 — 9 — — — — —9 — — 9 Adhesion promoters EBECRYL7100 — 10 4 6 2 — — — 4 4 4 4 4 4EBECRYL8402 0.5 — — — — 3.5 0.5 0.5 0.9 0.9 — 0.9 0.9 — Thermo- MEHQ 0.10.2 0.1 0.2 0.1 0.2 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 polymerizationinhibitor Surfactant UV3500 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.10.1 0.1 0.1 Photopolymerization IRGACURE 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.54.5 4.5 4.5 4.5 4.5 4.5 initiators 819 DAROCURE 4.5 4.5 4.5 4.5 4.5 4.54.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 TPO DETX 1 1 1 1 1 1 1 1 1 1 1 1 1 1Pigment dispersion PEA + pigCyan 10 10 10 10 10 10 10 10 10 10 10 10 1010 15% Total 100.7 105.3 103.2 101.3 105.2 98.8 100.7 102.7 100.1 100.1103.2 100.1 102.1 123.2 Viscosity at 20° C. [mPa · s] 25.1 34.5 32.228.9 30.5 34.8 25.2 25.6 32.9 29.4 33.7 24.8 25.2 34.9 Viscosity at 40°C. [mPa · s] 10.1 13.9 12.8 11.6 12.5 14.1 10.2 10.3 13.1 11.8 13.6 10.210.2 14.3

Details of components shown in Table 1 were as described below.

Monofunctional Polymerizable Compounds

V#192: phenoxyethyl acrylate available from Osaka Organic ChemicalIndustry Ltd.

FA-512AS: dicyclopentenyloxyethyl acrylate available from HitachiChemical Co., Ltd.

FA-511AS: dicyclopentenyl acrylate available from Hitachi Chemical Co.,Ltd.

Vinylcaprolactam available from BASF Japan Ltd.

Bifunctional Polymerizable Compounds

DPGDA: dipropyleneglycol diacrylate available from Shin-NakamuraChemical Co., Ltd.

TPGDA: tripropyleneglycol diacrylate available from Osaka OrganicChemical Industry Ltd.

TEGDA: triethyleneglycol diacrylate available from Osaka OrganicChemical Industry Ltd.

A-DCP: dimethyloltricyclodecane diacrylate available from SartomerCompany.

Adhesion Promoters

EBECRYL 7100: an amino acrylate available from DAICEL-CYTEC Co., Ltd.

EBECRYL 8402: an amino acrylate available from DAICEL-CYTEC Co., Ltd.

Thermal Polymerization Initiator

MEHQ: methyl ether hydroquinone available from Kanto Chemical Co., Inc.

Surfactants

UV3500: a polydimethylsiloxane surfactant available from Byk ChemieJapan K.K.

Irgacure 819: a photopolymerization initiator available from CibaSpecialty Chemicals Inc.

Dacocure TPO: a photopolymerization initiator available from CibaSpecialty Chemicals Inc.

DETX: diethylthioxanthone available from Nippon Kayaku Co., Ltd.

Colorant and Dispersant

C. I. Pigment Blue 15:4: a cyan pigment available from DIC Corporation.

PEA: a polyoxyalkylene-added polyalkyleneamine available from Dai-ichiKogyo Seiyaku Co., Ltd.

A colorant, a dispersant, PEA, and a cyan pigment were blended into apigment dispersion. The content of the cyan pigment in the pigmentdispersion was 15% by mass.

An ink composition was prepared in each example or comparative examplein such a manner that components shown in Table 1 were blended at aratio shown in Table 1 and were dissolve by mixing the components at 30minutes at room temperature and the mixture was filtered through a 5-μmmembrane filter. In Table 1, the content of each component in the inkcomposition is expressed in parts by mass.

All the obtained ink compositions were measured for viscosity at 20° C.and 40° C. with a viscometer, MCR-300, available from Nihon SiberHegnerK.K. The viscosities thereof were summarized in Table 1.

2.2. Evaluation Tests

2.2.1 Extensional Viscometer

A cylindrical portion was formed by expanding each ink composition so asto have a free surface parallel to the expanding direction of the inkcomposition. The rate of change S in width of the cylindrical portionwith time was measured in the expanding direction thereof. In theexamples and the comparative examples, an extensional viscometer, CaBER1, available from Thermo Haake Inc. was used.

2.2.2. Fitting

A technique for determining a, b, and c in Equation (1) by expandingeach ink composition with the extensional viscometer is described below.FIGS. 1A to 1C are illustrations showing the ink composition beingexpanded.

With reference to FIGS. 1A to 1C, the extensional viscometer includes apair of cylindrical jigs 10 arranged opposite each other, a laser lightsource 12, and a detector 14 facing the laser light source 12, the laserlight source 12 and the detector 14 being arranged perpendicularly tothe direction in which the jigs 10 are arranged. The jigs 10 have adiameter of, for example, 1 mm to 10 mm. In the examples and thecomparative examples, the diameter of each jig 10 was 6 mm.

The jigs 10 are spaced from each other at a distance L0 as shown in FIG.1A. In the examples and the comparative examples, the distance L0between the jigs 10 was 1 mm. A composition 20 is placed between thejigs 10. The distance between the jigs 10 is increased to a specificlevel as shown in FIG. 1B. The moving rate of the jigs 10 is, forexample, 0.01 m/s to 1 m/s. In the examples and the comparativeexamples, the moving rate of the jigs 10 was 0.05 m/s and the distanceL1 between the moved jigs 10 was 4 mm. That is, in the examples and thecomparative examples, the time taken for the distance L0 to increase tothe distance L1 was 60 ms.

The width D of the composition 20 is measured with the laser lightsource 12 and the detector 14 while the jigs 10 are being moved awayfrom each other. The width D thereof can be plotted with respect to timewith an analysis software program attached to the extensionalviscometer. The rate of change S in width can be also plotted withrespect to time with the attached analysis software program on the basisof the width D at a specific point in time.

In the examples and the comparative examples, the rate of change S inwidth was plotted with respect to the width D of the composition 20placed between the unmoved jigs 10 and was fit to a quadratic functionwith the attached analysis software program or another computer by themethod of least squares. Obtained results were substituted into Equation(1), whereby the values of a, b, and c were determined. In the examplesand the comparative examples, fitting was performed in such a mannerthat the origin of the time t was set to the point in time when thewidth D was reduced to about 20% to 25% (that is, about 1.5 mm) of avalue before the distance between the jigs 10 was increased. Since theorigin of the time t was set as described above, the ink composition inthe cylindrical portion was in an expansion fluid state, resulting in anincrease in accuracy of fitting.

FIG. 2 is a graph showing results obtained by fitting the inkcomposition prepared in Example 1. The abscissa and ordinate of thisgraph represent the time t (s) and the rate of change S in width D,respectively.

2.2.3 Properties of Ink Compositions

Table 2 shows the values of a, b, and c of the ink composition preparedin each of the examples and the comparative examples. The extensionalviscometer can be used to measure the time ts (s) taken until thecomposition 20 is broken. Table 2 also shows the time ts of the inkcomposition prepared in each of the examples and the comparativeexamples.

TABLE 2 Evaluation results Fitting results a b c ts (s) of satellitesExamples 1 S = −1137.1t² − 8.1037t + 0.2174 1137 8.1 0.22 0.0107 Good 2S = −1159.8t² − 8.156t + 0.211 1160 8.2 0.21 0.0104 Good 3 S = −873.27t²− 8.7206t + 0.1941 873 8.7 0.19 0.0107 Good 4 S = −826.19t² − 7.42t +0.2134 826 7.4 0.21 0.0122 Good 5 S = −897.21t² − 12.91642t + 0.1664 89712.9 0.17 0.0082 Good 6 S = −800.9t² − 13.562t + 0.1672 801 13.6 0.170.0083 Good 7 S = −822.97t² − 9.1393t + 0.1947 823 9.1 0.19 0.0288 Good8 S = −1076.3t² − 8.6105t + 0.218 1076 8.6 0.22 0.0108 Good Comparative1 S = −490.46t² − 8.4598t + 0.2286 490 8.5 0.23 0.0146 Bad Examples 2 S= −463.53t² − 8.94421t + 0.2235 464 8.9 0.22 0.0143 Bad 3 S = −547.56t²− 8.4708t + 0.2155 548 8.5 0.22 0.0136 Bad 4 S = −644.14t² − 8.5984t +0.2142 644 8.6 0.21 0.0127 Bad 5 S = −571.7t² − 8.2384t + 0.2152 572 8.20.22 0.0135 Bad 6 S = −472.66t² − 8.619t + 0.2234 473 8.6 0.22 0.0145Bad

As shown in Table 2, for the ink compositions of all the examples, a is800 or more, b is 7.4 to 14, and c is 0.16 to 0.22. For the inkcompositions of all the comparative examples, a is less than 800. Forthe ink compositions of Comparative Examples 1, 2, and 6, c is greaterthan 0.22. For the ink compositions of all the examples and thecomparative examples, the time ts (s) taken until the composition 20 isbroken is 0.1 s or less. For the ink compositions of Examples 5 and 6,the time ts is 0.01 s or less.

2.3. Print Evaluation

The ink composition of each of the examples and the comparative exampleswas introduced into a black column of an ink jet printer, PX-G5100,available from Seiko Epson Corporation. The ink composition was ejectedfrom the ink jet printer, whereby a test pattern was printed on arecording medium, having an A4 size, prepared by cutting a polyvinylchloride sheet, SPVC-G-1270T, available from Roland DG Corporation.

The test pattern was observed with an optical microscope and wasevaluated for the presence of satellites. A test pattern having nosatellite was rated as A. A test pattern having a satellite was rated asB. Table 2 shows the evaluation results. Those having satellites areprobably due to mist generated during ejection.

As is clear from Table 2, the ink compositions of the examples all showno satellite because a, b, and c in Equation (1) are 800 or more, 7.4 to14, and 0.16 to 0.22, respectively. In contrast, the ink compositions ofthe comparative examples all show satellites because a in Equation (1)is less than 800.

The ink compositions of the examples are prepared so as to have aviscosity of 25 mPa·s to 35 mPa·s at 20° C. The cylindrical portion isformed by expanding each ink composition so as to have a free surfaceparallel to the expanding direction of the ink composition and the rateof change S in width of the cylindrical portion with time is measured inthe expanding direction thereof. The ink composition is controlled suchthat a, b, and c are 800 or more, 7.4 to 14, and 0.16 to 0.22,respectively, when the rate of change S in width of the cylindricalportion with time t (s) is fit to a quadratic function given by Equation(1). Therefore, the rate at which the width of the cylindrical portionformed by expanding each of the ink compositions of the examples isreduced is sufficiently large and the ink compositions of the examplescan be stably ejected from ink-ejecting heads of ink jet recordingapparatuses and can provide high-quality images in which print positionsare hardly displaced or which are less affected by satellites.

The invention is not limited to the above embodiments. Variousmodifications can be made within the scope of the invention. Theinvention includes configurations (for example, configurations havingfunctions, methods, and results identical to those described in theembodiments and configurations having objects and effects identical tothose described in the embodiments) substantially identical to thosedescribed in the embodiments. The invention also includes configurationsin which portions not essential for the configurations described in theembodiments are replaced with others. The invention includesconfigurations that exhibit advantageous effects identical to thosedescribed in the embodiments or that can achieve objects identical tothose described in the embodiments. Furthermore, the invention includesconfigurations in which known techniques are added to the configurationsdescribed in the embodiments.

What is claimed is:
 1. An ejecting method comprising: ejecting acomposition from an ink jet head, the composition comprising at leastone monofunctional(meth)acrylate and at least one of abifunctional(meth)acrylate, wherein the composition has a viscosity of25 mPa·s to 35 mPa·s at 20° C., and a rate of change (S) in the width ofa cylindrical portion with time that is formed by expanding thecomposition, the width being measured in the expanding directionthereof, so as to have a free surface parallel to the expandingdirection of the composition defined by the quadratic equation:S=−at ² −bt+c  (1) wherein a, b, and c are 800 or more, 7.4 to 14, and0.16 to 0.22, respectively, and t is the time in seconds; wherein: adriving frequency F of the ink jet head is 1 kHz to 200 kHz; the ink jethead includes a nozzle for ejecting the composition, the nozzle having adiameter of 1 μm to 50 μm.
 2. The ejecting method according to claim 1,wherein the rate of change S is based on a width of the cylindricalportion at the beginning of expansion.
 3. The ejecting method accordingto claim 1, wherein a time taken to reduce the width of the cylindricalportion to zero is within 0.1 second from the beginning of expansion. 4.The ejecting method according to claim 1, wherein the compositioncomprises at least one polymerizable compound and at least onephotopolymerization initiator.
 5. The ejecting method according to claim1, wherein the ink jet head includes a multilayer piezoelectric elementand is operated in a longitudinal mode.
 6. The ejecting method accordingto claim 1, wherein the monofunctional(meth)acrylate contains at leastone of phenoxyethyl acrylate, dicyclopentenyloxyethyl acrylate, ordicyclopentenyl acrylate.
 7. The ejecting method according to claim 1,wherein the bifunctional(meth)acrylate contains at least one ofdipropyleneglycol diacrylate, tripropyleneglycol diacrylate,triethyleneglycol diacrylate, or dimethyloltricyclodecane diacrylate. 8.The ejecting method according to claim 1, wherein the ratio of theamount of monofunctional(meth)acrylate to the amount ofbifunctional(meth)acrylate is between 0.6 and 1.1.
 9. The ejectingmethod according to claim 1, wherein the composition contains an aminoacrylate.
 10. The ejecting method according to claim 1, wherein thecontent of the monofunctional(meth)acrylate in the composition is lessthan 30% by mass.
 11. The ejecting method according to claim 1, furthercomprising applying an ultraviolet ray to the composition.
 12. Theejecting method according to claim 11, wherein the dose of theultraviolet ray is in the range of 50 mJ/cm² to 15,000 mJ/cm².
 13. Theejecting method according to claim 1, further comprising applying anultraviolet ray to the composition using an ultraviolet light-emittingsemiconductor device.
 14. The ejecting method according to claim 1,wherein the composition further comprises a vinylcaprolactam.
 15. Theejecting method according to claim 1, wherein the composition furthercomprises pigment.
 16. The ejecting method according to claim 3, whereinthe content of the pigment in the composition is 0.1 to 25% by mass andhas an average particle size of 10 nm to 200 nm.